US20050232842A1 - Method for the production of endohedral fullerenes - Google Patents

Method for the production of endohedral fullerenes Download PDF

Info

Publication number
US20050232842A1
US20050232842A1 US10/519,696 US51969605A US2005232842A1 US 20050232842 A1 US20050232842 A1 US 20050232842A1 US 51969605 A US51969605 A US 51969605A US 2005232842 A1 US2005232842 A1 US 2005232842A1
Authority
US
United States
Prior art keywords
graphite electrodes
inert gas
modified
reactive gas
gas mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/519,696
Inventor
Lothar Dunsch
Petra Georgi
Frank Ziegs
Heidi Zoeller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
Original Assignee
Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV filed Critical Leibniz Institut fuer Festkorper und Werkstofforschung Dresden eV
Assigned to LEIBNIZ-INSTITUT FUER FESTKOERPER-UND WERKSTOFFFORSCHUNG DRESDEN E.V. reassignment LEIBNIZ-INSTITUT FUER FESTKOERPER-UND WERKSTOFFFORSCHUNG DRESDEN E.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUNSCH, LOTHAR, GEORGI, PETRA, ZIEGS, FRANK, ZOELLER, HEIDI
Publication of US20050232842A1 publication Critical patent/US20050232842A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/154—Preparation

Definitions

  • the invention relates to a method for synthesizing endohedral fullerenes in an arc reactor by burning off graphite electrodes.
  • the inventive method ensures a very high yield of fullerenes.
  • the fullerenes synthesized can be used, for example, as contrasting agents for medical examinations.
  • the inventive method is characterized in that the burning off is carried out in an atmosphere, which contains a reactive gas component, consisting of at least two elements, in an inert gas or mixture of inert gases.
  • the proportion of the reactive gas component may amount to 5% by volume up to 60% by volume. Preferably, it is 5% by volume up to 10% by volume.
  • a nitrogen-containing or carbon-containing reactive gas component such as ammonia or methane or other hydrocarbons, is used.
  • the reactive gas component may be supplied to the arc reactor during the burning off or generated in the arc reactor.
  • Graphite electrodes which are modified with metal or metal oxides, can be used for the inventive method.
  • graphite electrodes may be used, which are modified, for example, with holmium or scandium or their oxides.
  • graphite electrodes which have been modified with metal or metal oxides and a nitrogen-containing substance, can also be used.
  • a metal cyanamide preferably calcium cyanamide or lead cyanamide, can be used to modify the graphite electrodes with a nitrogen-containing substance.
  • fullerenes synthesized in this way, may be used, for example, as contrasting agents for medicinal investigations.
  • holmium metal-modified graphite electrodes are burned off with a pulsed DC current with a current strength between 75 A and 150 A in a gas mixture, which contains a reactive gas component.
  • the graphite electrodes used have a composition, in which the molar ratio of graphite to holmium is 1:0.4.
  • the gas mixture consists of helium and ammonia, the ammonia being the reactive component.
  • the proportions in the gas mixture are 200 mbar of helium and 20 mbar of ammonia.
  • endohedral holmium nitride cluster fullerenes are formed in a yield between 85 and 95%.
  • Ho 2 O 3 -modified graphite electrodes are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of between 75 A and 150 A.
  • the graphite electrodes used have a composition, in which the molar ratio of graphite to M 2 O 3 is 1:0.3.
  • the gas mixture consists helium and ammonia, the ammonia being the reactive component.
  • the proportions in the gas mixture are 200 mbar of helium and 20 mbar of ammonia.
  • Scandium- and CaNCN-modified graphite electrodes are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of between 75 A and 150 A.
  • the graphite electrodes used have a composition, in which the molar ratio of graphite to scandium to CaNCN is 1:0.6:0.4.
  • the gas mixture consists of helium and ammonia, the ammonia being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 10 mbar of ammonia.
  • endohedral holmium nitride cluster fullerenes are formed in a yield between 80 and 90%.
  • Graphite electrodes modified with Ho 2 O 3 and CaNCN are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of between 75 A and 150 A.
  • the graphite electrodes used have a composition, in which the molar ratio of graphite to Ho 2 O 3 to CaNCN is 1:0.4:0.4.
  • the gas mixture consists of helium and ammonia, the ammonia being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 10 mbar of ammonia.
  • endohedral holmium nitride cluster fullerenes are formed in a yield between 50 and 70%
  • Graphite electrodes are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of 150 A.
  • the gas mixture consists of helium and methane, the methane being the reactive component.
  • the proportions in the gas mixture are 200 mbar of helium and 10 mbar of methane.
  • CH 2 @C 70 is obtained as main component of the endohedral fullerenes, C 60 and C 70 representing the main propulsion of the total fullerene content.

Abstract

Method for synthesizing endohedral fullerenes it an arc reactor by burning off graphite electrodes, characterized in that the burning off is carried out in an atmosphere, which contains a reactive gas component, consisting of at least two elements, in an inert gas or inert gas mixture.

Description

  • The invention relates to a method for synthesizing endohedral fullerenes in an arc reactor by burning off graphite electrodes. The inventive method ensures a very high yield of fullerenes. The fullerenes synthesized can be used, for example, as contrasting agents for medical examinations.
  • Methods of synthesizing endohedral fullerenes in an arc reactor by burning off modified graphite electrodes are already known.
  • In the case of one of these methods, graphite electrodes, which are modified with one or more metals, are burned off in an atmosphere of flowing helium containing a small amount of nitrogen in an arc reactor for the Krätschmer-Huffman method (U.S. Pat. No. 6,303,760 B1), endohedral metal fullerenes of the type A3-nXn@Cm being obtained. The yield of endohedral metal fullerenes, obtained by this method, is very small; it is said to be between 3 and 5% (Stevenson, S. et al., Small-bandgap endohedral metallofullerenes in high yield and purity, Nature 401, 55-57 (1991)).
  • It is an object of the invention to provide a method for synthesizing endohedral fullerenes in an arc reactor by burning off graphite electrodes, with which it is possible to increase the yield of fullerenes significantly.
  • This objective is accomplished with the method presented in the claims.
  • The inventive method is characterized in that the burning off is carried out in an atmosphere, which contains a reactive gas component, consisting of at least two elements, in an inert gas or mixture of inert gases.
  • The proportion of the reactive gas component may amount to 5% by volume up to 60% by volume. Preferably, it is 5% by volume up to 10% by volume.
  • According to an advantageous development of the method, a nitrogen-containing or carbon-containing reactive gas component, such as ammonia or methane or other hydrocarbons, is used.
  • The reactive gas component may be supplied to the arc reactor during the burning off or generated in the arc reactor.
  • Graphite electrodes, which are modified with metal or metal oxides, can be used for the inventive method.
  • Accordingly, graphite electrodes may be used, which are modified, for example, with holmium or scandium or their oxides.
  • According to an advantageous development of the inventive method, graphite electrodes, which have been modified with metal or metal oxides and a nitrogen-containing substance, can also be used.
  • Especially a metal cyanamide, preferably calcium cyanamide or lead cyanamide, can be used to modify the graphite electrodes with a nitrogen-containing substance.
  • With the inventive method, a very high yield of fullerenes of 50 to 95% of endohedral M3N cluster fullerenes as main product is attained. The cost of carrying out the method is low and the method can be carried out easily and leads to reproducible results.
  • The fullerenes, synthesized in this way, may be used, for example, as contrasting agents for medicinal investigations.
  • The invention is explained in greater detail below by means of examples.
    • EXAMPLE 1
  • In an arc reactor, holmium metal-modified graphite electrodes are burned off with a pulsed DC current with a current strength between 75 A and 150 A in a gas mixture, which contains a reactive gas component. The graphite electrodes used have a composition, in which the molar ratio of graphite to holmium is 1:0.4. The gas mixture consists of helium and ammonia, the ammonia being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 20 mbar of ammonia.
  • When this method is carried out, endohedral holmium nitride cluster fullerenes are formed in a yield between 85 and 95%.
    • EXAMPLE 2
  • Ho2O3-modified graphite electrodes are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of between 75 A and 150 A. The graphite electrodes used have a composition, in which the molar ratio of graphite to M2O3 is 1:0.3. The gas mixture consists helium and ammonia, the ammonia being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 20 mbar of ammonia.
  • When this method is carried out, endohedral holmium nitride cluster fullerenes are formed in a yield of 60%
    • EXAMPLE 3
  • Scandium- and CaNCN-modified graphite electrodes are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of between 75 A and 150 A. The graphite electrodes used have a composition, in which the molar ratio of graphite to scandium to CaNCN is 1:0.6:0.4. The gas mixture consists of helium and ammonia, the ammonia being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 10 mbar of ammonia.
  • When this method is carried out, endohedral holmium nitride cluster fullerenes are formed in a yield between 80 and 90%.
    • EXAMPLE 4
  • Graphite electrodes modified with Ho2O3 and CaNCN, are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of between 75 A and 150 A. The graphite electrodes used have a composition, in which the molar ratio of graphite to Ho2O3 to CaNCN is 1:0.4:0.4. The gas mixture consists of helium and ammonia, the ammonia being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 10 mbar of ammonia.
  • When this method is carried out, endohedral holmium nitride cluster fullerenes are formed in a yield between 50 and 70%
    • EXAMPLE 5
  • Graphite electrodes are burned off in an arc reactor in a gas mixture, which contains a reactive gas component, with pulsed DC with a current density of 150 A. The gas mixture consists of helium and methane, the methane being the reactive component. The proportions in the gas mixture are 200 mbar of helium and 10 mbar of methane.
  • When this method is carried out, CH2@C70 is obtained as main component of the endohedral fullerenes, C60 and C70 representing the main propulsion of the total fullerene content.

Claims (11)

1. Method for synthesizing endohedral fullerenes it an arc reactor comprising burning off graphite electrodes, in an atmosphere which contains a reactive gas component, and providing said reactive gas component with at least two elements in an inert gas or inert gas mixture.
2. The method of claim 1, wherein the inert gas or the inert gas mixture includes 5% by volume to 60% by volume of reactive gas component.
3. The method of claim 1, wherein the inert gas or the inert gas mixture includes 5% by volume to 10% by volume of reactive gas component.
4. The method of claim 1, wherein the inert gas or inert gas mixture includes a nitrogen-containing or carbon-containing reactive gas component.
5. The method of claim 1, wherein the reactive gas component includes of ammonia or methane or of other hydrocarbons.
6. The method of claim 1, wherein the reactive gas component is supplied to the arc reactor from outside during the burning off or is generated in the arc reactor.
7. The method of claim 1, wherein graphite electrodes are used which are modified with metal or metal oxides.
8. The method of claim 7, wherein the graphite electrodes which are used are modified with holmium or scandium or their oxides.
9. The method of claim 1, wherein the graphite electrodes which are used are modified with metal or metal oxides and a nitrogen-containing substance.
10. The method of claim 1, wherein the graphite electrodes which are used are modified with metal cyanamide.
11. The method of claim 1, wherein the graphite electrodes which are used are modified with calcium cyanamide or lead cyanamide.
US10/519,696 2002-07-22 2003-07-21 Method for the production of endohedral fullerenes Abandoned US20050232842A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10233566 2002-07-22
DE10233566.4 2002-07-22
PCT/DE2003/002501 WO2004016624A2 (en) 2002-07-22 2003-07-21 Method for the production of endohedral fullerenes

Publications (1)

Publication Number Publication Date
US20050232842A1 true US20050232842A1 (en) 2005-10-20

Family

ID=30010328

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/519,696 Abandoned US20050232842A1 (en) 2002-07-22 2003-07-21 Method for the production of endohedral fullerenes

Country Status (8)

Country Link
US (1) US20050232842A1 (en)
EP (1) EP1523450A2 (en)
JP (1) JP4603358B2 (en)
CN (1) CN1671620B (en)
AU (1) AU2003250801A1 (en)
DE (2) DE10301722B4 (en)
RU (1) RU2004137099A (en)
WO (1) WO2004016624A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090250661A1 (en) * 2008-01-18 2009-10-08 Stevenson Steven A Trimetallic Nitride Clusters Entrapped Within CnN Heteroatom Cages

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2008317422A1 (en) 2007-10-22 2009-04-30 Luna Innovations Incorporated Metallofullerene contrast agents
CN101337668B (en) * 2008-08-11 2013-10-23 彭汝芳 Method for preparing embed fullerene
DE102008043654A1 (en) 2008-11-11 2010-05-20 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Diagnostic and / or therapeutic agent, process for its preparation and use
CN102205958B (en) * 2011-05-04 2013-01-23 中国科学技术大学 Method for preparing fullerene internally embedded with nitride clusters
CN104129775B (en) * 2014-07-16 2015-12-30 苏州大学 A kind of preparation method of embedded scandium oxide compound cluster soccerballene
CN106744814A (en) * 2016-12-06 2017-05-31 河南科技学院 A kind of extracting method of embedded metal fullerene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300203A (en) * 1991-11-27 1994-04-05 William Marsh Rice University Process for making fullerenes by the laser evaporation of carbon
US6171451B1 (en) * 1997-01-13 2001-01-09 Daimlerchrysler Aerospace Method and apparatus for producing complex carbon molecules
US6303760B1 (en) * 1999-08-12 2001-10-16 Virginia Tech Intellectual Properties, Inc. Endohedral metallofullerenes and method for making the same
US6787794B2 (en) * 2001-08-13 2004-09-07 Hitachi, Ltd. Quantum computer

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05282938A (en) * 1992-02-28 1993-10-29 Idemitsu Kosan Co Ltd Manufacture of metal stored fullerene and the like
US5876684A (en) * 1992-08-14 1999-03-02 Materials And Electrochemical Research (Mer) Corporation Methods and apparati for producing fullerenes
JPH06199509A (en) * 1993-01-07 1994-07-19 Nippon Telegr & Teleph Corp <Ntt> Method for stabilizing superfine particles, superfine particles wrapped with graphite and production thereof
DE4335915A1 (en) * 1993-10-21 1995-04-27 Roggenkamp Karl Heinz Process for producing fullerenes and doped Buckmister fullerenes from carbon-containing granular materials and dusts and the addition of metals or rare earths, where the raw material to be vaporised is located in a cup-like high-temperature-resistant case
JPH07189040A (en) * 1993-12-27 1995-07-25 Nec Corp Production of cylindrical graphite fiber
JPH09309711A (en) * 1996-03-18 1997-12-02 Toyo Tanso Kk Carbon cluster, raw material for producing the same and production of the same carbon cluster
DE19627338A1 (en) * 1996-06-28 1998-01-02 Hahn Meitner Inst Berlin Gmbh Electrode for the production of higher fullerenes using the Krätschmer-Huffman arc process
JP2000159514A (en) * 1998-11-26 2000-06-13 Univ Nagoya Production of metal-including fullerene

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5300203A (en) * 1991-11-27 1994-04-05 William Marsh Rice University Process for making fullerenes by the laser evaporation of carbon
US6171451B1 (en) * 1997-01-13 2001-01-09 Daimlerchrysler Aerospace Method and apparatus for producing complex carbon molecules
US6303760B1 (en) * 1999-08-12 2001-10-16 Virginia Tech Intellectual Properties, Inc. Endohedral metallofullerenes and method for making the same
US6787794B2 (en) * 2001-08-13 2004-09-07 Hitachi, Ltd. Quantum computer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090250661A1 (en) * 2008-01-18 2009-10-08 Stevenson Steven A Trimetallic Nitride Clusters Entrapped Within CnN Heteroatom Cages

Also Published As

Publication number Publication date
DE10393502D2 (en) 2005-07-07
AU2003250801A8 (en) 2004-03-03
CN1671620B (en) 2010-05-26
AU2003250801A1 (en) 2004-03-03
JP2005533745A (en) 2005-11-10
WO2004016624A3 (en) 2004-05-21
WO2004016624A2 (en) 2004-02-26
DE10301722B4 (en) 2009-12-10
JP4603358B2 (en) 2010-12-22
EP1523450A2 (en) 2005-04-20
CN1671620A (en) 2005-09-21
RU2004137099A (en) 2005-07-10
DE10301722A1 (en) 2004-02-05

Similar Documents

Publication Publication Date Title
TW200730245A (en) Catalyst for producing carbon nanotubules by decomposition of gaseous carbon compouds at a heterogeneous catalyst
CA2385802A1 (en) Method and apparatus for producing single-wall carbon nanotubes
US20050232842A1 (en) Method for the production of endohedral fullerenes
WO2003022739A3 (en) Apparatus and method for nanoparticle and nanotube production, and use therefor for gas storage
AU571355B2 (en) Pressure swing adsorption of carbon monoxide
BR0209426A (en) Protective gaseous mix useful for mig brazing of galvanized steel, and process with metal and inert gas (mig) for brazing galvanized steel
ATE330905T1 (en) PRODUCTION OF SINGLE WALL CARBON NANOTUBE
DE60222417D1 (en) PROCESS FOR PREPARING HYDROXYLAMMONIUM
MX9606441A (en) Non-stoichiometric tungsten carbide.
RU98103521A (en) IRON POWDER CONTAINING PHOSPHORUS AND METHOD FOR PRODUCING IT
ATE342904T1 (en) ARTIFICIAL OXYGEN CARRIER AND PRODUCTION PROCESS THEREOF
FI20011327A0 (en) Method for Purification of Gasification Gas
JP2002097004A (en) Method for manufacturing boron nitride nanotube by using oxide catalyst
JPS62265112A (en) Production of graphite intercalation complex
KR100771848B1 (en) Monodispersed highly crystallized carbon nanotubes and there&#39;s manufacturing method
JP3353068B2 (en) Method for producing heterofullerene in which part of carbon skeleton is substituted by boron and nitrogen
IT9020860A1 (en) END OF GAS PURIFICATION PROCEDURE
JP4155658B2 (en) Manufacturing method of carburizing atmosphere gas and carburizing method using the gas
JPS57101000A (en) Preparation of ceramic whisker
JPH03502749A (en) Gas used for CO2 laser and working method using CO2 laser
JP2639687B2 (en) Method for producing acicular silicon nitride
WO2004067446A1 (en) Sumanene and process for production thereof
JPH08188406A (en) Composite carbon nanotube whose ends are closed and its production and closing of opening of carbon nanotube
JPH0477399A (en) Production of sic whisker
KR100663717B1 (en) Method for Mass Production of Thin Multiwall Carbon Nanotubes Using Chemical Vapor Deposition

Legal Events

Date Code Title Description
AS Assignment

Owner name: LEIBNIZ-INSTITUT FUER FESTKOERPER-UND WERKSTOFFFOR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DUNSCH, LOTHAR;GEORGI, PETRA;ZIEGS, FRANK;AND OTHERS;REEL/FRAME:016316/0098

Effective date: 20050106

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION